Process for treating citrus pulp



Oct. 22, 1957 J. M. BoNNr-:LL

PROCESS FOR TREATING crTRus PULP 2 Sheets-Sheet l Filed April 24. 1953 Oct. 22, 1957 J. M. BONNELL 2,810,649

PROCESS FOR TREATING CITRUS PULP Filed April 24. 1953 2 Sheets-Sheerl 2 ATTORNEYS assignments, to Minute Maid Corporation, New York,

N. Y., a corporation of Florida Application April 24, 1953, Serial No. 350,891

6 Claims. (Cl. 992) This invention relates to the treatment of dried citrusv pulp for the recovery of glucosides, such as hesperidin', therefrom, and for the production of a substantially glucoside-free cattle feed product. More particularly, the invention relatesto improvements in the treatment of dried citrus pulp .to effect selective extraction of glucosides, such as hesperidin, and a limited amount of sugar therefrom, in the form of an ammoniated extract, and the simultaneous production of ammoniated substantially glucoside-free cattle feed products. The invention includes an improved process of treating dried citrus pulp to produce improved cattle feed products.

The dried citrus pulp which is treated by the presentv process is pulp such as results from the pressing of citrus waste to remove a large portion of the water therefrom and the drying of the pressed pulp. Citrus wastes are commonly admixed with a small amount of lime and ground and permitted to stand for a time, and then sub jected to pressing to remove a large portion of the water therefrom, and with subsequent dryingV to form al dried citrus pulp. The water removed by the pressing operation is commonly concentrated to form so-called citrus molasses.

Such dried citrus pulps contain glucosides in appreciable amount. Orange pulp contains hesperidin as its principal glucoside. Grapefruit pulp contains naringin as its principal glucoside. Other citrus pulps contain other glucosides. Ordinary dried citrus pulp such as results from liming and subsequent drying contains a relatively high content of sugars, but only a limited amount of nitrogen or protein, e. g., around 6% crude protein.

The process of the present invention extracts the glucosides from the dried citrus pulp together with a limited extraction of sugars, leaving the sugar content of the pulp largely unextracted. And both the resulting pulp and the extracted sugars are in the form of ammoniated products of relatively high protein-equivalent content.

According to the present invention, the dried citrus pulp is subjected to reaction and limited extraction with an excess of liquid ammonia at a low temperature, around the boiling point of liquid ammonia, to effect a limited and partial extraction of the pulp, together with a reaction of the liquid ammonia with the constituents of the pulp. An excess of liquid ammonia at low temperature and in a short time reacts with the dried pulp to form ammoniated products, some of which are readily soluble in excess ammonia, including the glucosides such as hesperidin. By regulating the amount of excess liquid ammonia, the glucosides such as hesperidin can be readily and substantially completely extracted, together with a limited amount of sugars, while leaving the main portion of the dried pulp in its reacted ammoniated condition. By withdrawing the excess liquid ammonia solution, the ammoniated product is freed from its glucoside content and also freed from a small and regulated amount of its ammonia content while leaving the ammoniated pulp, from which the excess liquidl ammonia solutionis re- VUnited States Patent O moved, in the form of a valuable ammoniated cattle feed product, which can readily be freed from excess ammonia. l

In carrying out the process, the dried citrus pulp is intimately admixed with an excess of liquidammonia at a low temperature and the liquid ammonia is permitted to react with the pulp for a short time. The reaction of the liquid ammonia with the dried pulp is an exothermic reaction, but by using an excess of liquid ammonia the heat of reaction is neutralized by the vaporization of some of the excess liquid ammonia, so that the temperature is maintained at a low temperature, around the boiling point of liquid ammonia, during the reaction. The vaporized ammonia, vaporized by the heat of reaction and by the heat of the added citrus pulp, is recovered in a suitable ammonia recovery system for reuse.

After the reaction of the citrus pulp with the excess liquid ammonia has taken place, the excess liquid ammonia, with its dissolved glucosides, and with a limited amount of dissolved sugars, is separated from the remainder of the pulp, giving a solution in liquid ammonia of the glucosides and of extracted sugars in the form of an ammoniated product. This liquid ammonia solution is an intermediate product of the process and is advantageously treated for the `recovery therefrom of the glucosides and of the sugars or ammoniated sugars.

The ammoniated product remaining after theremoval ofthe excess liquid ammonia extract will still be wet with the liquid ammonia and is treated to remove the excess ammonia-therefrom, which can readily be accomplished by moderate heating and with collecting and recovery` of they ammonia vapors for reuse in the process. The heating of the product does not, however, completely free it from an ammonia odor. The residual ammonia odor is undesirable from a cattle feed point of view and is also irritating. lt can, however, readily be removed by adding an acidied liquor such as a dilute acid solution.

The dried citrus pulp does not need to be completely freed from water but may contain a normal content of e. g. around 10% of water or even up to around 20% of moisture or somewhat more. The presence of a small amount of water in the pulp does not appear to interfere with the reaction and extraction operation.

The amount of liquid ammonia used for treating the dried pulp can be varied. A sucient excess should be used not only to insure reaction with the pulp but also to effect extraction of the glucosides and a limited extraction of the sugars. If too large an amount of liquid ammonia is used and the reaction and extraction are continued too long, a large and undesirable proportion of the sugars will be dissolved and extracted and removed, leaving a corresponding reduced amount of sugars in the ammoniated product after the removal of the extract therefrom. It is desirable to limit the amount of excess liquid ammonia so that the sugars are extracted only to a limited extent, leaving the major portion of the sugars behind in the extracted product. Thus, in continuous extraction of the dried citrus pulp with liquid ammonia, the amount of liquid ammonia may be around 1080 pounds for each 500 pounds of dry solids in the pulp treated.

The time required for the reaction of the liquid arnmonia with the dried citrus pulp and for effecting the extraction of the glucosides and a limited amount of sugars is relatively short. A time as short as 5 minutes appears to be entirely sufficient, and a longer time of up to around 20 minutes or somewhat more also is satisfactory;

In carrying out the process, it is advantageous to maintain effective agitation of the mixture of pulp and'liquid ammonia toinsurethorough and intimate contact and- Patented Oct. 22, 1957 reaction, particularly where a limited amount of excess liquid ammonia is used.

The present process has the advantage that it can be carried out at atmospheric. pressureY and at alow temperature, around the boiling point of liquid ammonia, 28 V1:". The temperature is self-maintaining because the heating elfect of the added citrus'pulp and-the heat of reaction will vaporize some. of theexcess liquid arnmonia, which can be recovered in an ammonia absorptionsystem for reuse. The process canalso be carried out at pressures lower than atmospheric 'and also as pressureshigher than. atmospheric, vbut .the useofvacuum or pressure apparatus-Which would-bey requiredin Vsuch cases isunnecessary when the. .processisa carried out-at atmospheric pressure. The apparatus in. whichfthe reaction. is. carried. out should, of: course,l be adequately insulated or laggedto avoid Aheat lossesandzto'minimize theyaporiation ofliquid ammonia. w

The reactions which. take. place-between. the citrus pulp and the liquid ammonia result inxtheformationof reaction products in which the. ammonia isv chemically combined in the form of additionor. reaction products. The glucosides such as hesperidinand. naringin appear to he converted into solubleammonia compounds, solublev in the liquid ammonia. The sugars alsoappear to: be. largelyl comb'inedwithrthek ammonia, asindicatedfbythe relatively high nitrogen content of -both the extractedA product and of the sugars .contained in the extract.

The extracted'product,. remaining after theV removal ofY thev aqueous ammonia extract, is separately. treated by -moderate heating to remove. excess ammonia and, treatment -with an acid to x or. remove the ammonia odor, and'is a valuable ammoniated cattlev feed with areltively, high content of combined nitrogen or protein equivalent containing-v e. g. aroundA 14% crude protein.. equivalent and'1U% moisture.

The combinedv reaction and extraction .process can' be carried out as a batch operation by. admixing the. dried' citrus -pulp with an excess of'liquidamrnonia.and.` permitting the mixture to stand with or withoutagitation for a few minutes before withdrawing the extract from the residue. The extract containingthe glucosides and a limited amount ofsugar can be separately treated, as. abatch operation or by a continuous `process, vto separate. the glucosidesfrom the sugars. The extracted product, still moist with-liquid ammonia, is separately treated by moderate heating to remove the excess ammoniaand' by then adding a small amount of an acid. liquon to neutralize the ammoniaodor, and' is then a product.

ready for shipment and use as an ammoniatedy cattle. feed.

TheA process can advantageously be carried out,'.however, as. a continuous process, with continuous Vsupply of the dried'citrus pulp and liquid ammonia, withcontinuous agitation of thev mixture to insure reaction and partial'extraction, with drawing offandrecoveryk of` am-V monia vaporized during the reaction andv extraction, withl drawing.olf and recovery of ammonia-vaporized during; the reaction and extraction, with continuous drawing'otf of the extract from the. residue, and with continuous. heating of'the.residue to removeexcess ammonia therefrom, and nally with continuous addition of aqueousacid materialto remove the ammonia-odor.

`Th"e present invention also. provides an improved. process for treating the liquid ammonia extract, contain ing the glucosides such as hesperidin andpart' of the sugars to'separate the glucosides therefrom. This .separa-- tion is' advantageously effectedby first heating-the extractto drive` loffth'e ammonia 'therefrom`moreorless com-- pletely and Withrecovery ofi the ammonia vapors in=a1 suitable.: ammo-nia recovery system. To the resulting.; mixture of ammoniated sugar and glucoside, water'is added to.- form :aqueous solution, thisV solution is"a`cidied to -set tfree the:glucoside/fand*` to initiate .crystallization of theglucoside fromthe aqueousso'lution; By permitting:

the acidiied solution to stand, the crystallization of the glucoside such as hesperidin is substantially complete, and the removal of this product by filtration leaves an ammoniated aqueous sugar solution which can advantageously be concentrated to syrupy consistency and added to the extracted residue after it has been freed from excess ammonia.

The return of the ammoniated sugar extract in this way and its admixture with the extracted product gives aiinalproduct which contains substantially all of the constituents of the original'feedy except tnek glucosides in the form of the ammoniated' products. The return of the concentrated ammoniatedsugar so1ution, after separating the glucosides, for admixture with the extracted residue, will serve to neutralizeany ammonia odor and make unnecessary the addition of an acid solution for that purpose. If the amount of water added with the concentrated liquid makes the product too moist, it can be further dried to its desired moisture content by a separate drying operation.

In-carrying out the process, ammonia vapors "are given off duringfthe reactionand extracting step-ofthe process as wellf as in the' heating of the extracted residue to remove ammonia ktherefrom andl also from the extract when the liquidammoniais removed therefrom. These ammoniafvapors from the` varioussteps of the process are advantageously combined andpassed to an ammonia condenser to condense theammonia to liquid ammonia for reuse or to one or another of the known and available types. of.ammonia recovery systems where the arnmonia. .vaports can be recovered and reconverted into liquid ammonia for further use in the-process.

The invention-will be further described in connection with theaccompany drawings, in which:

Figure 1y isa flow sheet illustrating the process and the-various -steps andsequence of steps, and

Figure 2 shows,v in. a` somewhat `diagrammatic and conventional'manner,an arrangement of apparatus for carrying out the process. It will be understood that the specific description, and the particular arrangement of apparatus shown illustrate the invention but that the invention is not limitedthereto.

y In the owsheet ofv Figure l; the'dry citrus pulp and theliquid ammonia are shown .as supplied to the extractorreactor, .in whichthereaction ofthe'liquid ammonia with the pulp takes place and in which-the extraction of the glucoside and .thelimited amountof sugar by the liquid ammonia also takes. place. In generaLthe amount of thc volume of liquid ammonia is desirably inI excess of the volume of .dry citrus .pulpf so astoinsure dissolving of the glucoside. The. mixture of. liquidammoniaV and.y pulp is desirably, agitated .to promote .reaction and extraction.

This reactionand extraction. operation, when'carried out at atmospheric. pressure,results.in1boilingoff of some of 'the'liquid ammonia due to the sensible heating of the added drycitrus pulp which is higherf than-the boiling point of vkliquidammonia, anddue to the heat of reaction between the ammonia and the sugars and other constituents-of theA pulp. The ammonia vapors thus boiled olf from the extractor-reactor are vpassed toanfammonia recovery system.

The reactionand extraction which takes place inthis first-step of the process results' inthe production of'two produots'which are separatedffrom eachother-one being the liquid ammoniatextra'et containing theglucosiderand` a? limited amount of sugarv which,l as shown in 'the flow sheet,.is.p`assed to' anammonia evaporatorfand residuey dissolver, and the other'being thetreactionproduct remaining after the liquid ammonia` extra'ctlhasibeen' drawn off` of?` which tends lto be held in the porousreaction-product` until driven oif by moderate heating. This heating which drives off the excess ammonia doesnot'free the product from a residual'ammonia odor which persists even after prolonged heating, and which is undesirable from a cattle feed point of view. To remove this undesirable ammonia odor from the product, it is passed from the evaporator to a humidifier and deodorizer Where an acid or acid material is added to remove the ammonia odor, and Where water is Vadded to give a product of proper moisture content suitable for use as a finished cattle feed product, e. g., around more or less.

Where an aqueous solution of sulfuric or phosphoric acid or of an acid phosphate is added to the product in the-humidifier and deodorizer, the product can be directly produced with the ammonia odor removed and of proper moisture content.

In the ow sheet, theliquid ammonia extract containing the glucoside and a limited amount of sugar is heated in the ammonia evaporator to drive off the liquid ammonia more or less completely and the ammonia vapors so driven off are passed to the ammonia recovery system. Some water will ordinarily be contained in the dry citrus pulp treated and will be admixed with the extracted materials after the driving off of most or all of the liquid ammonia. The product thus freed from the liquid ammonia solvent will contain the glucoside in the form of an ammonia compound and will also contain the extracted sugars largely if not entirely in the form of arnmonia reaction compounds.

In order to separate the glucoside, Water is added to dissolve the extracted products to form a water solution. And this solution is passed to the acidifier where the solution is aciditied by adding sucient acid, e. g., sulfuric acid, to give an acid pH and to set free the glucoside from its combination with ammonia. The freed glucoside is relatively insoluble, even in the presence of the sugar compounds and, by proper acidification and agitation, crystallization of the glucoside will begin and can be continued by passing the acidiiied product to a holding tank and holding it until the glucoside has been substantially precipitated. Y

By passing the resulting product through a filter, the glucoside is filtered off and recovered and an aqueous solution of sugar compounds is then passed to an evaporator and evaporated to give a concentrated ammoniated sugar product. The solution after filtering is an acid solution part or all of which can be returned, as shown in the dotted line, to the humidifier and deodorizer for neutralizing the ammonia odor and adding moisture to the extracted reaction product. Similarly the solution after concentration, and which is also acid in character, can be returned in part or in whole as shown in dotted lines to the humidifier and deodorizer for admixture with the extracted ammoniated residue. If the amount of unconcentrated or concentrated solution thus returned gives a wet mixture containing too much water, the mixture can be further dried to remove excess Water, to give the iinished feed a proper moisture content.

By returning all of the ammoniated sugar solution, or all of the concentrated ammoniated sugar solution, after filtering off the glucoside, and admixing it with the extracted ammoniated residue, a composite ammoniated product is produced which contains all of the ammoniated citrus pulp treated, except the glucosides which are extracted and removed. And since acid is added to acidify the solution before crystallizing the glycoside, and a further amount of acidmay be added to neutralize the ammonia odor of the extracted product, the final cattle feed will also contain ammonia compounds of the added acid.

The amount of such ammonia compounds of added acid will .vary with .theamountof acid required to acidify the extract to setfree the glucoside. If all of the liquid ammonia is Ldrivenofffrom the solution before the residue is dissolved in water and acidified, only a small amount Y of acid islrequired to give the aqueous solution a desirable pH e. g. of around 4. If some of the liquid ammonia remains in the product, due to incomplete removal, this excess ammonia will also require neutralization by acid and a larger amount of acid will be required in this case, with the corresponding increase in the amount of arnmonium compounds formed by neutralization of this acid.

In the flow sheet, the ammonia vapors given off from the extractor-reactor, from the evaporator and from the ammonia evaporator are all shown as going to an ammonia recovery system. Various ammonia absorption systems can be used for condensing or recovering this ammonia. The passage of the ammonia vapors through a condensor maintained at a temperature sufficiently below the boiling point of ammonia will serve to condense and liquefy the ammonia vapors so that they can be returned to the process. Ammonia absorption refrigeration plants areavailable for recovering the ammonia and converting it to liquid ammonia. Ammonia compression and compression systems combined with refrigeration, can also be used, such systems commonly operating at considerably higher pressures than atmospheric.

Figure 2 shows -an arrangement of apparatus for carrying out the process in a continuous manner,.with continuous supply of the dry citrus pulp and liquid ammonia to the extractor-reactor, continuous drawing off of the liquid ammonia extract, continuous removal of excess ammonia from the extracted ammoniated pulp and continuous admixture of an acid to remove the ammonia odor from the product so that the ammoniated cattle feed product can be directly produced in a continuous manner.

The apparatus for treating the extract for the separation of the glucoside from the ammoniated sugar solution is shown as carried out batchwise, with alternating receivers for the extract to accumulate batches which arel separately and successively treated. Y

One of the valuable citrus pulps, which contains hesperidin as its principal glucoside, is orange pulp, and in the following detailed description of the apparatus and the carrying out of the process therein, the dried citrus pulp referred to is dried orange pulp so that hesperidin is the glucoside extracted and recovered as a valuable product of the process.

In the apparatus of Figure 2, the extractor-reactor 1 is horizontally arranged with a broken iiight screw conveyor 2 therein and an end plate or wier 3 near the discharge end over which the extracted pulp passes to the discharge portion 4. A sight glass 5 is provided to show the liquid level during the extraction and reaction.

The dried orange pulp is contained in the feed hopper 6 and supplied therefrom through the feed conduit 7 by a variable speed screw conveyor 8 for regulating the rate `of continuous supply of the dried pulp to the extractor-reactor.

A supply of liquid ammonia is provided in the liquid ammonia tank 10 which has a supply pipe 11 for supplying liquid ammonia thereto. A liquid ammonia pipe 12 leads from the tank 10 through the flow meter 13 to two branch pipes 14 and 15. The main flow of liquid ammonia is through the branch pipe 14 to supply the liquid ammonia for the reaction and extraction. A small amount of liquid ammonia is supplied through the branch pipe 15 to wash the pulp leaving the reaction and extraction treatment.

Ammonia vapors given off in the extractor-reactor are passed through the pipe 16 to an ammonia condensor shown conventionally at 17 for cooling and condensing the ammonia vapors and lreturning them as liquid ammonia to the tank 10.

The liquid ammonia extract is drawn oif from the extractor-reactor through the pipe 19 having valve 1S therein to one or the other of two boilers 20 and 21.

From the extractor-reactor, the extracted reaction product passes over the end plate or wier 3 into the discharge monia3 usedlfor washing the-pulp. This/liquidammonia will alsocontainextracted material" and passes through thepipe v29 tomix'withtheextract goingto the boilerszt) or 2'1.

The discharge end r30of the evaporator' discharges the product; after --the removal'of-f excessammonia, toA the inlet` -311 of" aconveyor` chamber 32- having a broken'iiight screw conveyorf35ltherein and having'an acid-liquor tank 341locatednearthelinlet of-the chamber andfconnectedy to the chamber through the" feedtpipeeSS-havingyvalve 36 therein. Thel added acid'l solution orVv liquid is mixed with the mater-ialV passing through-they conveyor chamber tol neutralizethe objectionable' ammonia odor and togive the product aA desirable moisture content.

From thedischarge end'of this'conveyor chamber, the finished productisdischarged through the conduit 37 to a stationtS-for bagging orpaclcag-ing the. product, or for conveyingittoa-place-of storage;

In the operation-of theapparatus thus described,v liquid ammoniavwill be 'rst supplied tothe extractor-reactor to form a body of liquidi ammonia therein andY the dried orange pulp'will then be suppliediat aregulated rate and subjectedI to reaction and extraction; with the liquid ammonia, which will"be continuously suppliedinvproper proportion to maintain a continuous` reaction and extraction.

The-mixture of liquid ammonia and'pulp willbe kept inv agitation by the broken i'ght'screw conveyor-whichwill' cause the pulp to progress fromthe feed end tothe discharge end of! the extractor-reactor, where it Ywill be carriedup-by theA blades ofthe conveyor and discharged over the end plate 3 into the discharge portion 4.

the extractionand reaction, willA` be conveyed bythe pipe 16 to the condensing system 17.' The liquid 'ammonia extract will be continuously drawn ott through the pipe 19 to one or the other ofthe boilers 20fand 21', The ammoniated extracted product discharged' froml the extractor-reactory will be-washed lwith a small' amount of liquid ammonia. supplied through the branchpipe 'and the resulting solutionvandany excess liquid ammonia discharged with the product will ilow throughthe screen 27 land be united with the main liquid ammonia extract.'

In the evaporator 23 moderate heat will be supplied through the heating jacketv 25A and the material Will be kept agitated'by the broken ight'screw. conveyor so that the excess ammonia will be driven ofi to free theextracted product from excess ammonia.

The resulting product discharged intothe inlet 31 of the conveyor chamber 32 will have an objectionable ammonia odor'which willfbe neutralized and overcome by the addition of. a regulated amount of acid material. And if the proper amount of water is also added Withth'eracid the product which is subjected to repeated agitation in the screw conveyor chamber will-leave this chamber not only .free from ammonia. odor butalso oadesirable water content for a cattle feed, e. g., around 10%, more or less.

The process thusV far described is..a.continuous process, withcontinuous supply of the dry orange pulp, continuous supply. of 'liquid ammonia for the extraction and reaction, continuous evaporation of excess Iammonia from the extractedreaction product, continuous drawing oiand'condensation or recoveryofjammoniavapors from theextractor-reactorandevaporator and Icontinuous admixture of aqueous acidtoneutralize the ammoniaodor and'toV add a desirable amount ofjmoisturel to the product.

The ammonia Vcondensing system shown isa refriger- Ammonia vaporsboiled oilC fromthe liquidammonia during atedcondenser, cooled'A toax temperature' Ibelow that-ofi the boiling-point of liquid ammonia, e; g., around 40 F.- orflower, in which the ammonial vapors arecooledand condensed and liquefied with return ofthe liquid ammonia' to the supply tank 10; Added ammonia can'be added through thefeedpipe 11 to make up forthe ammonia" usedin the process.

A certain amountv of` air andv moisure are introduced`V into the system during the process, e. g., with the citrus pulp, and some air and moisture will beadmixedwith the ammonia vapors from the process. These must be purged from the system. The purge arrangement shownis a pipe 41 leading fromthe topV of the tank 10'and`hav.- ing valve 42 therein and leading to acondensorV 43" for cooling and condensing ammonia which returns as liquid* ammonia to the tank 10 and with the gases then passing through the pipe 4 4 to a water scrubber' tower.v or pipe 45 supplied with'water spray from the pipe 46 and'with a discharge outlet for the ammonia waters shown'atV 47.

The liquid ammonia extract produced in the extractorreactor'is drawn to one or the other of the two boilers 20 and 2'1, one boiler being filled, while the other is being heated, and these boilers operating alternately rather than continuously. This liquid ammonia extract contains the sugars largely or entirely as ammoniated sugars and contains the; hesperidin as a soluble ammonium compound and also contains a small amount of water.

Each of thel boilers 20 and 21 is connected'with the. pipe leading the liquid ammonium extract from the. extractor' reactor so that each boiler can beused alternately. Each boiler has a jacket connected to a steam 1ine.51 withA valve 52 therein so that each boiler can be, heatedindependently. The condensate from the heating jacket'passes off through the drain pipe 54;.

Each boiler has an ammonia'vapor outlet'55ileadi'ng to.

motor 63. The draw-olf lines are connected to the pump.64 for pumping the solution through the line 65 to a digestor 66 having a steam jacket with steam-inlet line 67 and condensateline 68 and with an agitator driven by the motor 69.

An acid tank 70 isconnected through the line 71 with valve 72 therein yfor introducing an acid in regulated. amount to the digestor 66. The outlet line 73 from the. digestor with valveV 74 therein leads to the. pump 75.*which. discharges the liquid through the line 76 to the/largel tank 77 where crystallization of the hesperidin takes. place.

From the tank 77 the liquid ilowsr throughthe. line. 78 to the pump 79 and is pumped. through. the line. 80. having valve 81 therein to a lter 82, such as a normal plate or frame or other type of filter, for filtering off the hesperidin which is recovered at 83, while the filtered liquid passes. through the line 84 to an evaporator 85V and' is heated to form aconcentratedv orl viscous solution and discharged through the line 86 to storage 87, or. may be returned as indicatedin the diagrammatic flow sheet, Figure.1,.for admixture with the dried extracted ammoniated product.

Inv theoperation of the apparatus for treatingthe. liq-y uid ammonia extract', this extractis run first into one of the boilerswhere it is heated to boil olf the ammonia which passes to the ammonia recovery system, leaving the ammoniated extract with som'e admixed water in the. boiler.. Water is then added to theboilerf. to dissolve the ammoniated product and form anaqueoussolutionwhich.

to set free the hesperidin, the amount added being such as to give a pH of about 4. This acidied solution is held in the digestor for a period of time to bring aboutv initial crystallization of the heperidin and is then transferred to the crystallizing tank where it is held for a period of several hours and allowed to cool to effect substantially complete crystallization of the hesperidin, which is removed by the filter, leaving an aqueous solution Substantially free from hesperidin.

As an illustrative example of the carrying out of the process in the apparatus described there is fed to the extractor-reactor dry orange pulp and liquid ammonia at the rate of, e. g. about 500 pounds of pulp (dry solid base) and 1200 pounds of theliquid ammonia per hour, of which approximately 1080 pounds goes to the extractorreactor through the line 14 and approximately, 120 pounds is used as a final rinse for the extracted product through the line 15.

The extracted and washed ammoniated product is passed through the evaporator 23 to remove excess ammonia and the resulting product is mixed with a limited amount of acid liquor in the conveyorchamber 32 to produce around 480 pounds of finished ammoniated pulp of around 15% crude protein equivalent, calculated on the solids, and around 10% moisture. The amount of dried material going to the conveyor chamber 32 represents around 430 pounds of ammoniated feed solids and, with the addition of about 50 pounds of acid liquor, gives around 480 pounds of the finished product.

Ammonia vapor from the extractor-reactor and also from the evaporator pass to the ammonia recovery system where the ammonia is condensed and returned to the ammonia tank.

The liquid ammonia extract drawn olf from the extractor-reactor, when the rate of feed and liquid ammonia supply is as indicated above, is a solution containing around 735 pounds of liquid ammonia, around 76 pounds of solids in the form of ammoniated sugars and hesperidin and around 50 pounds ofwater. That is, where the hourlyrate of feed of orange pulp solids and liquid ammonia is that indicated'above per hour, the rate of ammonia extract produced per hour is illustrated by the figures indicated.

This liquid ammonia extract is run into one or the other of the boilers where the ammonia is boiled olf and returned to the ammonia recovery system. For the amount of ammonia solution referred to above, containing about 76 pounds of solids and 50 pounds of water, there is added, after the ammonia has been boiled away, around 450 pounds of water to dissolve the solids and the resulting solution is then run into the digestor where it is held for approximately 2 hours at 140 to 160 F. and is, prior to this holding, adjusted to a pH of 4 with sulfuric acid. The amount of 96% sulfuric acid may be as little as 1 pound where the ammonia is substantially completely removed from the boiler, or may be a considerably larger amount where some of the ammonia remains behind and requires neutralization with the acid.

After holding in the digestor for from l to 2 hours, the material is transferred to the crystallizing tank where it is held for around l to l2 hours, moreor less, and allowed to cool to effect substantially complete crystallization of the hesperidin, or until no more crystals appear after filtering a small sample of the solution. After this cooling and crystallization for the proper length of time it is pumped'through the filter, giving, for example, about 5 fpounds of hesperidin and a solution containing around 70po`unds` of ammoniated sugars, which when evaporated will produce a concentrated solution of about 72 brix and containing an amount of nitrogen corresponding to around 55% crude protein equivalent, based on the solids.

The two boilers are so arranged that each boiler holds, for example, the liquid ammonia extract produced in one hours time, and the boilers are used alternately. These boilers have sufficient heat transfer surface to furnish in about l hour or somewhat less.

VAfter all of the ammonia is removed from the boiler, v

the water is added to dissolve the solids, or admix solids and water, left in the boiler and the amount of water should be such as togive a workable solution, avoiding an unnecessary excess which would require added evaporation of water after the crystallization of the hesperidin.

With a limited and partial extraction of ammoniated sugars along with the hesperidin, while leaving the major portion of the ammoniated sugars behind in the extracted residue, the amount of ammoniated sugars in the aqueous extract is such that the hesperidin can be crystallized therefrom. A

The use of an excessive amount of liquid ammonia is undesirable because it tends to extract a larger proportion of the ammoniated sugars and to leave less of the ammoniated sugar in the extracted residue.

In the operation of the process in a continuous manne the time of holding of the reaction mixture in the extractor-reactor for effecting the reaction of the liquid ammonia with the pulp and for effecting extraction of the hesperidin and of a limited amount of ammoniated sugar can be varied, e. g., between 5 and 20 minutes, more or less.

reactorV is a-satisfactory period of time. But a shorter period of time is suflcient to effect substantially complete that it is readily extracted in a relatively short period of g time provided there is sucient agitation to insure thorough penetration and extraction of the granular pulp of the liquid ammonia.

The press liquid containing the ammoniated sugars, after removal of hesperidin, may either be evaporated to give a thick molasses-like product, or may'be used in part to acidify the ammoniated and extracted pulp in the screw conveyor 32. Where the total amount of concentrated solution is added to, and admixed with, the ammoniated extracted pulp and the resulting mixture contains too much water for a satisfactory cattle feed, it can be further dried to remove the excess water. In this case, the cattle feed will contain the ammoniated products of the extracted pulp, and the ammoniated products from the solution, which together constitute substantially the entire pulp treated in an ammoniated condition except for the removal of the hesperidin. In this way, a finished cattle feed can be produced containing a large amount of combined nitrogen approximating 20% of crude proteinequivalent nitrogen.

Another use for the ammoniated product remaining after the removal of hesperidin is for admixture with citrus molasses to increase its protein-equivalent nitrogen content.

While the process has been described more particularly in connection with the treatment of dried orange pulp for the recovery of hesperidin as a valuable product of the process and for the production of a substantially hesperidin-free ammoniated pulp product, the process is also applicable to the treatment of other citrus pulp, e. g., to grapefruit pulp, for the production of naringin, or to other citrus pulps or mixtures of pulps for the production of glusosides therefrom.

The present .process has the advantage that it is an anhydrous process or substantially anhydrous for converting dried citrus `pulp to valuable glucoside-free dry ammoniated pulp products.

The present process has the further advantage that itl-' A period of about 20 minutes in the extractorthat* "overheating byA klieat Aof .reaction "or otherwi'se avoided.

the' glucoside andta limited*y amount. oftammoniated 'sugar hasfbeenf extracted b ur'whilr. retains iir tire-extracted* ammoniated"prodiict'th'exnajdrportionof'tlieamrnonited1 sugars,l as 'wellasotlerammoniatediconstltuents:

The* processl also lias "the, advantage tliat itA notA 'onlyh extracts the' glucoside*`but"eifcts^"oniy"a'partial' land limited extraction of sugars; 'giving anA extract which, after removal of the liquidv ammoniaY anddigestingin"` an acidifiedl aqueous solution; permits" crystallization' of: the glucoside in the presence of the ammoniated sugars' From' a product standpoint; the' present invention provides: not onlyfor the production'o Vhesperidin"or': ther glucoside, as a valuableprodetof the: process, but' also for the productionfof: ammoniatedl'cattle feed products substantially free 'from glucosid'es.

Onev of i the valuablev products is' theV extracted am'' moniatedipulp, freefrom glucosides'and fromta part only of 'the= ammoniatedsugars and being an ammorriated5pu1p with a high nitrogen and 'proteinequivalent content.

Another valuable product of `the` processistlie ammoniatedsugarextract' after* the crystallization' of' the glucoside therefrom, which-is avaluableammoniated sugar product. ItV is not only free from' glucoside; but has a very high nitrogen or proteineequiva-lent contentV andi is valuable for use in ad'mixturewithl othercattle'feedlproducts, including ordinary untreateddried citrus; pulp with'4 3 which it canV bey adrnixed and including' ordinary citrus molasses with-which it cank be admixed` to increase' the protein-equivalent content of such products;

Al valuable combinedprodu'ct voflthe process is the mixture of extractedk ammoniated'pulp andof' theconcentrated extracted portion of the pulp, after removal of glucoside. If 'all of the ammoniated sugar extract'is ad-I mixed With all of the extractedammoniated pulp, tlie product', in eliecncontains substantially allof'the original' pulp constituentsin an `ammoniatcd condition, except' for theremoval of the glucosides, such as hesperidin.

1. Themethod of treating dried'citrus pulp to .extract glucosides therefrom and to 'form'. anammoniat'ed .pulp product which comprises reacting the dried'pulp withan excess of liquid-ammonia at low temperatures -to effect' reaction of the4 liquid ammonia with the pulp and` to extractfrorn the. pulp glucosides and a'limitedv amount of the-.sugar ofthe pulp, separating the liquid ammonia ex# tract containing the glucosides and part' of the sugarsfrom the ammoniatedlpulp, heatingfthe ammoniated pulp totfree it fromexcesslanimonia, and treating'theercsulting4 ammoniatedpulp lproductwith an -a'cid tofr'ee'it from its-- ammonia odor.

'2; The. method-of: treating dried'citrus-pulp to-remove glueosides therefrom. and to for1n= an amm'oniatedpulp'v product which comprises admixingandireacting and extracting the pulp vwithan excess oflliquidammonia at-'atmospheric pressure andat approximately.the'boilingpointof liquidammonia, removing; the excess ammoniafwith extracted constituents including glucosides. andpartofithe. ammoniated sugarof the pulp, heating the extracted ammoniated pulp to remove excess ammonia therefrom and adding to the .resulting ammcniated pulp van aqueous acid solutionto remove'v the ammonia odori fromithe product'.

v 3h Thecontinuous v process` of ;treating ,dried f' citrus: pulp, for the extraction of glucosides and part ofitheammonia. therefromand to give anrammoniatedvpulp product ,which Y 12 comprisestcontiiiuously 'adding' and'. admixing the dried cituszpulp'andan excess of liquid'ammonia with agitationv ofthemixttu'c andmaintenance-of the mixtureat approxil n lmatelyfatrnosplieric'pressureand'tlie boiling point of liquid' ammonia/to' effect reaction of' the liquid' ammonia withv the pulp anda selective, extraction of`glucosides and. part' '10* :excess ammonia',jandcontiiiuously' admixing with the resulting pulp an.acidto remove the` ammonia odor from the.pulp.A

4. The method of recoveringglucosides, and aliquid'.r

ammoniated'sugar product from driedl'citrus. pulp which; y 15' comprises reactingtlie pulp with-'ann excess ofliquidLam:

monia at .approximately atmosphericl pressurejat. the boil.- ing point ofliquidammonia to elect reaction of the liquid. ammonia with the pulp and to. effect` partial. andjselective extraction of'glu'cosid'es and partoffthe, ammoniaV there,- from, drawingoft' the resultingiliquidl ammonia extract,.

sulting product in water to. frmtan. aqueous s0lution,..f

acidifyingv the. solutiony and crystallizing. the glucoside.

therefrom, and reconcentratingthe resultingamrn'oniated.A l sugar. so1ution..substantially freefr'om glucosides,..to form.

monia: therefrom, forming an..acidified,y aqueous solution.. from the resulting.. product. and. crystallizing7 hesperidinV` therefrom.. l v v Y,

6. The method of treating dried. orange. pulp for the.. n production of hesperidin andA an ammoniatedpulp prod-- uct therefrom which .comprises reacting.. and. extracting-,the pulp with4 an excess of liquidb ammoniay at approximately, atmospheric pressure and at approximately the tempera ture of boiling ammonia to1effect-,extraction-offhesperidin 5 and-part. of thesugars, as an.ammoniated.sugarf/product;L

-while leaving the. major. portion ofthe sugars-,unextractedf4 in the:ammoniatedproduch removing.y theliqpidammonia,v extract and freeing itr-V from liquid ammonia, formingganf acidiiied aqueousxsolutionfromethetresultingproductt andf.` ,crystallizing hesperidin.therefrom-separating,thehesperifH din from-the aqueous ammoniatedtsugar` solution, ;concen1r tratingk theresulting solution, heating;` the am'moniatcd residue frnmfwhich the; extractisr separated, freeing itt fromexcess ammonia.. and admixingthe concentratedam'.-

moniatedtsugarextract.with'the-extracted residue to free, it vfrom .itsaammoniatodorfandtto give a composite-product'.- containingbothfthelammoniated Lresidue andthe :extracted ammoniated sugarsti l 

1. THE METHOD OF TREATING DRIED CITRUS PULP TO EXTRACT GLUCOSIDES THEREFROM AND TO FORM AN AMMONIATED PULP PRODUCT WHICH COMPRISES REACTING THE DRIED PULP WITH AN EXCESS OF LIQUID AMMONIA AT LOW TEMPERATURES TO EFFECT REACTION OF THE LIQUID AMMONIA WITH THE PULP AND TO EXTRACT FROM THE PULP GLUCOSIDES AND A LIMITED AMOUNT OF THE SUGAR OF THE PULP, SEPARATING THE LIQUID AMMONIA EXTRACT CONTAINING THE GLUCOSIDES AND PART OF THE SUGARS FROM THE AMMONIATED PULP, HEATING THE AMMONIATED PULP TO FREE IT FROM EXCESS AMMONIA, AND TREATING THE RESULTING AMMONIATED PULP PRODUCT WITH AN ACID TO FREE IT FROM ITS AMMONIA ODOR. 